EP2238087B1 - Process for producing a granular material - Google Patents
Process for producing a granular material Download PDFInfo
- Publication number
- EP2238087B1 EP2238087B1 EP20090702966 EP09702966A EP2238087B1 EP 2238087 B1 EP2238087 B1 EP 2238087B1 EP 20090702966 EP20090702966 EP 20090702966 EP 09702966 A EP09702966 A EP 09702966A EP 2238087 B1 EP2238087 B1 EP 2238087B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel slag
- granular material
- slag particles
- process according
- carbonated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000008569 process Effects 0.000 title claims abstract description 52
- 239000002893 slag Substances 0.000 claims abstract description 144
- 239000002245 particle Substances 0.000 claims abstract description 117
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 81
- 239000010959 steel Substances 0.000 claims abstract description 81
- 239000004567 concrete Substances 0.000 claims abstract description 44
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 43
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004220 aggregation Methods 0.000 claims abstract description 22
- 230000002776 aggregation Effects 0.000 claims abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 7
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 7
- 235000010216 calcium carbonate Nutrition 0.000 claims abstract description 6
- 235000011160 magnesium carbonates Nutrition 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 15
- 239000003546 flue gas Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000005056 compaction Methods 0.000 claims description 10
- 239000011398 Portland cement Substances 0.000 claims description 8
- 150000001553 barium compounds Chemical class 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- 239000000463 material Substances 0.000 description 23
- 239000004568 cement Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000006703 hydration reaction Methods 0.000 description 16
- 230000036571 hydration Effects 0.000 description 15
- 229910052918 calcium silicate Inorganic materials 0.000 description 14
- 238000002386 leaching Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 229910001385 heavy metal Inorganic materials 0.000 description 11
- 239000004576 sand Substances 0.000 description 11
- 235000012241 calcium silicate Nutrition 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000007704 transition Effects 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000009736 wetting Methods 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- 150000004679 hydroxides Chemical class 0.000 description 6
- 235000012245 magnesium oxide Nutrition 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000032258 transport Effects 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- -1 fluorine Chemical class 0.000 description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RCMWGBKVFBTLCW-UHFFFAOYSA-N barium(2+);dioxido(dioxo)molybdenum Chemical compound [Ba+2].[O-][Mo]([O-])(=O)=O RCMWGBKVFBTLCW-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011376 self-consolidating concrete Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002926 BaMoO4 Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910003110 Mg K Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011395 ready-mix concrete Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
- C21B3/06—Treatment of liquid slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/142—Steelmaking slags, converter slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2400/00—Treatment of slags originating from iron or steel processes
- C21B2400/02—Physical or chemical treatment of slags
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/18—Carbon capture and storage [CCS]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- Granulated Blast Furnace Slag mainly formed by an amorphous phase of a mixture of calcium, silicon, aluminium and magnesium oxides formed after rapidly quenching the molten slag, at least can be used as a coarse aggregate in concrete compositions, or, in finely ground form (GGBFS), as a cement substitute.
- GGBFS finely ground form
- the fine fraction of slowly-cooled and therefore mainly crystalline slag has shown until now extremely negative properties of water absorption.
- Such slag contains ⁇ -dicalcium silicate, which has no binding properties, but on the other hand can absorb large quantities of water. This has deleterious effects, for instance, for the workability and durability of concrete if this slag is used as fine aggregate (i.e. as sand) or filler.
- crystalline lime-silicate slag generally comprises crystals of dicalcium silicate (CaO) 2 SiO 2 in both their ⁇ and ⁇ polymorphic states. As molten dicalcium silicate slowly cools down and solidifies, it goes through several polymorphic forms:
- the grains of the coarser granular material may have sizes up to and including y, y being larger than 2x, preferably larger than 3x, more preferably larger than 4x and most preferably larger than 5x.
- y being larger than 2x, preferably larger than 3x, more preferably larger than 4x and most preferably larger than 5x.
- said carbonation step may be performed in a continuous counter current flow process.
- said carbonation step may be artificially accelerated, for example, by carbonating with a gas, such as for instance a flue gas, comprising at least 5 vol.%, preferably at least 8 vol.% and more preferably at least 10 vol.% carbon dioxide. Both these features help achieving a more complete carbonation of the steel slag particles. Carbonating with industrial flue gases moreover provides an advantageous use to carbon dioxide that normally would otherwise be directly emitted into the atmosphere as a greenhouse gas.
- said carbonation step may be performed at a pressure lower than 10 bars and preferably substantially at ambient pressure.
- a pressure lower than 10 bars and preferably substantially at ambient pressure.
- a low pressure promotes crystal growth instead of crystal nucleation, this latter being known to give rise to very small carbonate crystals characterised by poor binding properties.
- low-pressure carbonation produces larger carbonate crystals, which strengthen the steel slag particles, and also entrap heavy metals, such as chromium or molybdenum, within the particles.
- a base in particular sodium and/or potassium hydroxide, is added to the steel slag particles prior to said carbonation step, in order to counteract the pH decrease due to carbonation and, if possible, buffer the carbonated steel slag particles at a pH higher than 11.5, more particularly higher than 12. It has been found that the chromium and molybdenum leaching is lowest if the pH is maintained roughly above 12, in particular between 12 and 13. Moreover, this additive has also been found to facilitate the hydration of amorphous calcium and magnesium oxides in said fine steel slag fraction.
- the present invention also relates to process for producing mortar or concrete by mixing the carbonated granular material with at least a hydraulic binding agent and with water.
- the particles bigger than 35 mm are then put back into the first crusher 9.
- the fraction of particles between 14 and 35 mm goes into a second crusher 17 and a second sieve 18, where after being crushed again it is separated into two fractions: a fraction of particles smaller than 14 mm and a fraction of particles bigger than 14 mm.
- the fraction of particles bigger than 14 mm is taken by a third conveyor belt through a second metal separating magnetic belt 20, where more metal 21 is removed, and back into the second crusher 17.
- a fine fraction 24 of particles smaller than 0.5 mm is particularly rich in ⁇ -dicalcium silicate, and is therefore used in a particular embodiment of the process of the invention, illustrated in Fig. 3 .
- the particles in said fine stainless steel slag fraction 24 are first aggregated to form a coarser granular material 25 with a granulometry between 0 and 4 mm, and then carbonated.
- the carbonated granular material 26 can then be used in a concrete mix with at least a hydraulic binder 27, such as ordinary Portland cement, and water 28, and this as a substitute, for example, of [0-4 mm] porphyry sand.
- a first breaking up step is carried out on those clods before the aggregation step.
- the fine fraction 24 is dried, then fed through a hopper 29 into a rotary harrow 30, and sieved to remove any remaining clods larger than 4 mm, which are then fed back into the hopper 29.
- Tables 1 to 4 show the results of hydration tests on calcinated (and thus substantially calcium and magnesium hydroxide-free) samples of the fine fraction 24:
- Table 1 Hydration with 20 wt. % pure water Hydration time [min] Mg(OH) 2 [wt. %] Ca(OH) 2 [wt. %] Total hydroxides [wt. %] 43 0.00 0.00 0.00 236 0.00 0.00 0.00 514 0.08 0.14 0.22 3000 0.11 0.10 0.21
- Table 2 Hydration with 20 wt. % of an aqu. solution of 0.5M Mg acetate Hydration time [min] Mg(OH) 2 content [ wt. %] Ca(OH) 2 content [ wt.
- the grain size of the coarser granular material 25 obtained in this aggregation step can be roughly controlled by regulating the flow of water 34 and the residence time of the slag particles in the pelletizer 31.
- the granular material 25 is fed into sieve 35 to remove oversize grains, in this particular embodiment those over 4 mm.
- a fine sieve could also be used to remove undersize grains, for instance those under 1 mm.
- Proctor density it is understood the compacted dry volumic mass of these aggregates, as determined, for example, but not necessarily, by the original Proctor compaction test, as described in ASTM D698 / AASHTO T99, which is incorporated by reference, and uses a 4-inch (10.2 cm) diameter mould which holds 1/30th cubic foot (850 cm 3 ) of granular or powdery matter, and calls for compaction of three separate lifts of this granular or powdery matter using 25 blows by a 5.5 Ib (2.49 kg) hammer falling 12 inches (30.5 cm).
- the water content will also be important for the carbonation of the particles, by facilitating the transport of the carbon dioxide reacting with the particles.
- this coarser granular material 25 is carbonated.
- this carbonation step may be carried out in a continuous manner, for instance within an inclined rotating drum 36 with a flue gas supply 37, and a flue gas exhaust 38.
- the granular material 25 is conveyed by gravity against the flow of flue gas in the drum 36.
- Said flue gas may be provided by, for instance, an incinerator, a power plant, a blast furnace or a cement kiln, at substantially atmospheric pressure and a temperature of around 50°C, with about 10 Vol.% CO 2 and a humidity of 98 %.
- the carbonation time can be regulated by the dimensions of the drum 36, its inclination and/or its rotation speed. It has been found that a substantial level of carbonation may be achieved in as little as 10 minutes. Although in this particular embodiment the carbonation is carried out continuously, alternatively it would also be possible to carry out batch carbonation instead.
- the flue gas exiting the rotating drum 36 through the flue gas exhaust 38 still contains a significant amount of carbon dioxide. Since highly basic process water, with a pH value which can exceed 12, may be effluent, for instance, from the previous crushing and washing of the steel slag, this flue gas can still be used to neutralise such effluent process water.
- the humidity of the flue gas in the drum is preferably controlled so as not to fall below 75%, to prevent drying out the granular material 25. Moreover, this humidity also ensures a more complete hydration of the calcium and magnesium oxides in the steel slag particles to produce the calcium and magnesium hydroxides which then react with the carbon dioxide in the flue gas to form calcium and magnesium carbonates.
- the calcium and magnesium carbonates bind the slag particles in each grain of the resulting carbonated granular material 26 together, providing significant mechanical strength. More importantly, these carbonates tend to heal the microcracks in the surface of the slag particles, significantly decreasing their ability to absorb additional water, and thus improving the workability of concrete and mortar mixtures incorporating this carbonated granular material 26 as a substitute for, for instance, sand.
- the maximum "surface dry" water content of untreated fine steel slag of abovementioned 0-0.5 mm fraction 24 has been measured according to European standard EN 1097-6 (or BS 812: part 2:1975) as being 36 wt. %. That of the same fine slag fraction, carbonated and aggregated, has been measured as 19.5 wt. %. Carbonation thus clearly reduces the water absorption of the steel slag particles.
- Tables 6 and 7 show the results of these comparative wetting and drying of, respectively, untreated fine steel slag and the carbonated granular material 26.
- the "surface dry" equivalent absorbed within the loose particles or grains has been calculated by subtracting from it the previously calculated water content adsorbed onto and between the loose particles and grains. Graphs corresponding to these results are also represented in Figures 5 and 6 .
- Table 6 Wetting and drying of untreated steel slag Time [min] Total water content [wt. %] "Surface dry" equivalent [wt.
- the carbonated granular material 26 because of its better drainage, also has a much lower water adsorption, considerably reducing its weight increase when wet, as well as the range of variation in total water content. This facilitates its handling and transport considerably.
- the carbonated granular material 26 shows improved heavy metal retention with respect to carbonated, but non-aggregated stainless steel slag particles, as shown by the results of molybdenum and chromium leaching tests according to DIN 38414-S4 carried out on both materials and reproduced on Table 8:
- Table 8 Heavy metal leaching in carbonated material Mo Cr [mg/l in leachate] [mg/l in leachate]
- Non-aggregated, carbonated particles 0.47 0.12 Granular material (first test) 0.20 0.12 Granular material (second test) 0.10 0.06
- the high chemical stability of calcium and magnesium carbonates compared with calcium and magnesium oxides or hydroxides, ensures the improved durability of the mortar or concrete produced using this carbonated granular material 26.
- Fig. 3 shows the grain size distribution curve of this carbonated granular material 26 compared with that of commercially available 0-4 mm porphyry sand 40 for construction. As can be seen in this graph, these materials show very similar grain size distributions.
- the carbonated granular material 26 has a bulk density of around 1350 kg/m 3 , which is considerably lower than the bulk density of such sand, which is around 1840 kg/m 3 .
- this is an advantageous side-effect, which can result in a reduction of transportation costs, as well as of the weight of structures built using the carbonated granular material 26.
- this carbonated granular material 26 is mixed with cement and water.
- Table 9 shows the compositions of three examples, A, B and C of such mortar and of two comparative examples, D and E, of conventional mortar produced using 0-4 mm porphyry sand.
- Mortar A comprises water, an ordinary Portland cement (CEM I), and a carbonated granular material 26, produced without addition of barium compounds and carbonated for approximately 3 hours
- mortars B and C comprise water, a carbonated granular material 26 produced with addition of barium hydroxide, and, respectively, different types of cement, namely the same ordinary Portland cement (CEM I) as mortar A, and a GGBFS cement (CEM IIIB).
- the two comparative mortars D and E comprise water, 0-4 mm porphyry sand, and, respectively CEM I, and CEM IIIB.
- These comparative examples follow the specifications of the EN-196/1 standard, namely, by weight, one part cement, three parts standard sand and half a part water, whereas in the examples containing carbonated granular material 26, the lower density of this carbonated granular material 26 has been taken into account, so that there is only two parts carbonated granular material 26 per part of cement.
- Table 9 Comparative mortar examples MORTAR CEMENT WATER/CEM. SAND/CEM. GRANULAR RATIO (WT.) RATIO (WT.) MATERIAL/CEM. RATIO (WT.) A CEM I 0.5 0 2 B CEM I 0.5 0 2 C CEM IIIB 0.5 0 2 D CEM I 0.5 3 0 E CEM IIIB 0.5 3 0
- Table 10 shows the results of these mechanical tests: Table 10: Bending and compression strength of mortar samples MORTAR BENDING STRENGTH [MPA] COMPRESSION STRENGTH [MPA] A 3.98 31.81 B 4.85 28.09 C 4.64 24.04 D 9.30 49.41 E 9.52 46.97
- Table 11 shows the results of these tests: Table 11: Molybdenum and chromium leaching under DIN 38414-S4 MORTAR MOLYBDENUM [MG/L] CHROMIUM [MG/L] A 0.10 ⁇ 0.10 B ⁇ 0.10 ⁇ 0.10 C 0.14 ⁇ 0.10
- the samples containing the carbonated granular material 26 present very good chromium and molybdenum retention characteristics, apt to satisfy even some of the most stringent environmental regulations. Whether barium compounds are used or not, these retention properties can also be improved by buffering the pH of the carbonated steel slag particles, so that it remains between 12 and 13.
- Leaching tests have been carried out on finely ground samples of mortar A in aqueous solutions of increasing acidity. In each test, 10 grams of finely ground mortar have been added to 100 ml of aqueous solution and shaken for 24 hours in a vibrating table. To decrease the pH of the mixture, aqueous solutions with increasing concentrations of nitric acid (HNO 3 ) have been applied.
- Table 12 Leachate of mortar A under increasing acidity conditions mg/l in leachate % acid (vol.) pH B Na Mg K Ca Cr Mo Ba 0 12.42 8.84 86.30 0.00 129.80 430 0.05 0.04 1 12.00 8.66 120.90 0.00 191.40 2994 0.13 0.15 4.81 3 10.79 20.93 136.80 0.00 153.60 8025 0.50 0.30 4.11 6 8.62 53.60 149.90 265.75 154.85 17295 0.44 0.90 5.91 9 7.85 111.0 223.30 1894.5 179.35 27285 0.03 1.26 12 3.30 255.2 283.75 4111.0 290.70 50050 4.32 0.02 13 1.93 275.5 143.05 1101.0 185.50 14510 69.10 1.50
- Table 12 thus shows how it is preferable to maintain a high pH in the mortar or concrete produced using the method of the invention. This can be achieved. for instance, by dissolving sodium and/or potassium hydroxides in the water 34 before its use in the aggregation step, and this in a concentration, for example, of about 0.05-0.5 mole/I, preferably 0.1-0.2 mole/I, and/or by using a basic process water effluent resulting, for instance, from slag treatment.
- Another possibility is the addition of a small amount, for instance 5 wt. %, of hydraulic binder, in particular of ordinary Portland cement, such as, for example, the abovementioned CEM I cement, to the steel slag particles of the fine fraction 24 prior to and/or during the aggregation step. Not only does this improve the mechanical properties of the resulting granular material, but also, due to the alkalinity of ordinary Portland cement, it also has an additional buffer action, and it also turns out to have an additional positive effect in reducing the leaching of both chromium and molybdenum.
- ordinary Portland cement such as, for example, the abovementioned CEM I cement
- the water content resulting in the maximum packing density may be determined by alternative tests, such as, for instance, the "Modified Proctor” test, ASTM D1557 / AASHTO T180, also incorporated by reference, which uses the same mould, but different compaction parameters, or other related tests using different moulds, compaction methods, or measuring systems.
- the carbonation could be also carried out using a chemical agent other than carbon dioxide, or in a state other than gaseous.
- the fine fraction of slag particles may also be more finely ground before the aggregation step.
- Said aggregation step may also be carried out by other means than the disc or pan pelletizer described hereabove, such as, for instance, a pelletisation press.
- a reducing agent such as, for example, iron (II) sulphate, in particular heptahydrated iron (II) sulphate (FeSO 4 .7H 2 O)
- the duration of the carbonation may be adjusted according to the circumstances, and the carbonation be carried out using different equipment than the rotating drum described hereabove. Accordingly, the description and drawings are to be regarded in an illustrative sense rather than a restrictive sense.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Glanulating (AREA)
- Processing Of Solid Wastes (AREA)
- Seasonings (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
Description
- The present invention relates to a process for producing a granular material for mixing with at least a hydraulic binding agent and with water to produce mortar or concrete.
- The steel industry produces large amounts of waste materials, in particular in the form of steel slag. The disposal of that waste is a significant problem, in particular for steel slag containing pollutants such as heavy metals, e.g. chromium, nickel, or molybdenum, and/or halogens, e.g. fluorine, which could constitute a significant environmental and health hazard, should they leach out into the environment, and in particular into water supplies and/or the food chain.
- Granulated Blast Furnace Slag (GBFS), mainly formed by an amorphous phase of a mixture of calcium, silicon, aluminium and magnesium oxides formed after rapidly quenching the molten slag, at least can be used as a coarse aggregate in concrete compositions, or, in finely ground form (GGBFS), as a cement substitute. However, the fine fraction of slowly-cooled and therefore mainly crystalline slag has shown until now extremely negative properties of water absorption. Such slag contains γ-dicalcium silicate, which has no binding properties, but on the other hand can absorb large quantities of water. This has deleterious effects, for instance, for the workability and durability of concrete if this slag is used as fine aggregate (i.e. as sand) or filler. As the γ-dicalcium silicate absorbs much of the water poured into the concrete mix, this fails to become fluid enough to be effectively poured, impairing its workability. Moreover, as the water trapped in the slag is released during the concrete setting process, it may form small voids to the detriment of its strength and durability.
- At ambient temperature, crystalline lime-silicate slag generally comprises crystals of dicalcium silicate (CaO)2SiO2 in both their β and γ polymorphic states. As molten dicalcium silicate slowly cools down and solidifies, it goes through several polymorphic forms:
- αwith hexagonal crystal structure,
- αH' with orthorhombic crystal structure,
- αL' with orthorhombic crystal structure,
- β with monoclinic crystal structure, and
- γ with orthorhombic crystal structure.
- As the last transition is linked to an increase of approximately 12% in volume, it causes high strains and microcracks in the dicalcium silicate crystals of the orthorhombic γ polymorphic state. These microcracks explain the disadvantageous water absorption properties that had been found hitherto in slag containing γ-dicalcium silicate, as water is absorbed by capillarity into them.
- The increase in volume in the transition from the β polymorphic state to the γ polymorphic state not only causes microcracks but even grain fracture and separation. As a result, the fine fraction of the slag will be disproportionately rich in comparatively soft γ-dicalcium silicate. Due to the abovementioned microcracks and the associated capillarity, this fine fraction of the slag will have a water absorption capacity of over 35%. Moreover, under comparatively humid conditions, it can retain this water for longer periods of time.
- In the article "The use of stainless steel slag in concrete", A. Kortbaoui, A. Tagnit-Hamou, and P.C. Aïtcin, Cement-Based Materials, p. 77-90, 1993, a process for producing mortar or concrete was proposed comprising the step of mixing at least a fine fraction of steel slag particles, containing a significant amount of γ-dicalcium silicate, with at least a hydraulic binding agent and with water to produce said mortar or said concrete. However, the amount used was limited by the negative effect of that fine fraction on the workability of the cement mix. Since the fine steel slag fraction can absorb large quantities of water, using the normal amounts of water in the mixture will result in a thick, nearly solid paste. In particular, this negative impact on the workability of the cement mix would make it inadequate for use in self-compacting concrete, as defined by the European Guidelines for Self-Compacting Concrete, published by the European Precast Concrete Organisation, the European Cement Association, the European Ready-mix Concrete Organisation, the European Federation of Concrete Admixture Associations and the European Federation of Specialist Construction Chemicals and Concrete Systems. Adding more water, however, will have a negative impact in the strength of the concrete, since a water film forms around each steel slag particle which will leave a void once the concrete hardens. Attempts to compensate this by adding plasticizer or cement will increase the cost.
- Moreover, in concrete production facilities, the water which is adsorbed onto the particles of the fine and coarse aggregates (since this water is readily available in the mortar or concrete mix) is taken into account when weighing the different ingredients of the concrete or mortar to be prepared but not the amount of water which is absorbed more strongly within these aggregates. The adsorbed water is more particularly determined by determining the "surface dry" density of the aggregates and by calculating the difference between the actual density of these aggregates and the "surface dry" density thereof. When the steel slag particles are dry, they absorb much water from the concrete or mortar composition thus resulting as explained hereabove in a bad workability. On the other hand, since the amount of water absorbed in the steel slag particles has a big effect on the density of the steel slag particles, the use of dry or wet steel slag particles will moreover have a considerable effect on the concrete or mortar composition as the different components are weighted. Our tests have revealed that the fine fraction of unquenched slag may absorb more than 35% by weight of water (determined on the basis of the "surface dry" weight, i.e. not including any water adsorbed onto the slag particles), whereas, after drying at 42°C, the water content may be less than one tenth of that. This results in a very broad water content range under real, rather than laboratory, conditions which in practice makes it very difficult to maintain consistent material parameters under various weather conditions, especially since the content of water absorbed within the slag particles in not taken into account when weighing the concrete or mortar ingredients. A drawback of a high water absorption is that the specific weight increase of water-saturated slag and the mortar or concrete mixes containing them results in higher transport costs and requires stronger casings when casting concrete.
- Also, the water absorbed within the slag particles may form pockets in the concrete or mortar containing them. These water pockets can render the finished material more vulnerable to frost. Finally, since slag may contain heavy metals, leaching remains a significant problem.
- In
EP 1 420 000 - For all these reasons, the fine fraction of unquenched slag containing γ-dicalcium silicate has proved, until now, very difficult to recycle.
- The problem addressed by the present invention is thus that of reducing the water absorption and leaching of heavy metals of a fine fraction of steel slag particles, containing a significant amount of γ-dicalcium silicate, so as to be able to increase the amount of this waste material that could be mixed with at least a hydraulic binding agent and water for producing mortar or concrete.
- This problem is solved by a process comprising an aggregation step and a carbonation step. In the aggregation step, steel slag particles from at least a fine fraction of steel slag, in particular a fine fraction of steel slag containing a significant amount of γ-dicalcium silicate, are aggregated into larger grains so as to form a coarser granular material. In the following carbonation step, the aggregated particles in said coarser granular material are carbonated by means of carbon dioxide so as to produce a carbonated granular material.
- By the combination of these steps, a material is obtained with a significantly lower water absorption and therefore significantly better workability when it is mixed with cement and water. The carbonation converts calcium and/or magnesium hydroxides into calcium and magnesium carbonate phases with binding properties that heal the microcracks in the fine steel slag particles, significantly reducing their water affinity, and bind them together within each grain, providing, already without any additional binder, a harder, coarser material than the original fine slag fraction with a much wider range of applications. The water content within these grains ("dry surface" water content) remains within a much narrower range throughout various different heat and humidity conditions, making its use in concrete and cement mixes much more practical under real conditions than that of untreated steel slag fines. Moreover, the carbonation step also provides with a means for capturing carbon dioxide which would otherwise be of concern due to its greenhouse effect, and traps the heavy metals within the grains, reducing the polluting leachate.
- Although in the Japanese patent publication application
JP 2001-026470 - In the paper "Accelerated carbonation of waste calcium silicate materials", presented at the Young Researchers Forum organised by the SCI Construction Materials Group and held 27 April 2000, a process was proposed to carbonate a fine fraction of steel slag particles, containing a significant amount of γ-dicalcium silicate, in a mould, so as to produce a hardened construction material in the form of briquettes.
- However, this process presents several disadvantages. First of all, due to the limited diffusion of the CO2 within the mould, this process is only suitable for producing small pre-cast construction parts. Moreover, even with such small parts, it is difficult to ensure that the material is carbonated evenly, usually leaving an insufficiently carbonated core with unsatisfactory mechanical and leaching properties.
- As an alternative, in Japanese patent application publication
JP 2003-212617 - With the process of the invention, however, since its product is a loose granular material, it will be possible to carbonate the fine steel slag fraction in advance, and obtain a granular material which is easy to store and handle before it is mixed with the hydraulic binder and water in a conventional manner.
- In the International patent application
WO 2007/096671 , a process had been proposed for producing mortar or concrete comprising the step of carbonating fine waste materials before mixing them with at least a hydraulic binding agent and with water. However, the waste materials mentioned are residues of quarrying and combustion processes, and it does not appear that it would have been evident for the skilled person that it would be advantageous, or even possible, to apply the same process to steel slag, and more specifically to a fine fraction of steel slag particles, containing a significant amount of γ-dicalcium silicate. - In the French
patent application FR 2 735 767 - Advantageously, the water content of said larger grains during the aggregation step is controlled, so that, at the end of said aggregation step, it is within a range of 5 wt. %, preferably 3 wt. %, above or below the optimum water content resulting in a maximum dry density in a Proctor compaction test performed in accordance with ASTM D698 / AASHTO T99 on the particles used to produce the larger grains. The Proctor density, that is, the dry density of a powdery or granular material measured according to a Proctor compaction test, indicates how closely its particles are packed and varies according its water content. It is thus possible, with Proctor tests at various moisture levels on the steel slag particles used in the process, to determine at which water content the particles will be more densely packed. By controlling the water supply before and/or during the aggregation step, or if necessary by drying the material, so as to obtain approximately the same water content in the granular material, it is possible to achieve the same optimum packing within the grains. More densely packed particles within the grains will result in harder grains after carbonation, with more strongly bonded particles. Within these ranges of water content values, it will thus be possible to achieve better density, packing and interface cohesive strength of the particles within each grain in the granular material. Moreover, additional water absorption will be reduced, which will improve the workability of the mixture with a hydraulic binder and water.
- Advantageously, the steel slag particles may have sizes not larger than x, said x being not larger than 4 mm, preferably not larger than 3 mm, more preferably not larger than 2 mm, and most preferably not larger than 1 mm. The steel slag particles of those sizes can be particularly rich in γ-dicalcium silicate, and thus more difficult to recycle by other means.
- Advantageously, the grains of the coarser granular material may have sizes up to and including y, y being larger than 2x, preferably larger than 3x, more preferably larger than 4x and most preferably larger than 5x. Such a coarser granular material can be more useful in a concrete mixture than finer particles, offer better flowability and workability, yet still be easy to store and handle as a loose material before the mixing step.
- However, y may be preferably smaller than 25 mm, preferably smaller than 20 mm and more preferably smaller than 15 mm. Since the carbonation step takes place after said aggregation step, this facilitates a more complete carbonation of the coarser granular material than if said grain size was larger.
- Advantageously, said coarser granular material may be agitated during said carbonation step, preferably in a substantially continuous manner. An improved, more homogeneous carbonation can be achieved in this manner.
- Advantageously, a hydraulic binder, in particular ordinary Portland cement (OPC), may be added to said steel slag particles prior to and/or during said aggregation step, in particular with a weight ratio to the steel slag particles between 1 and 10%. Besides an increase in the mechanical strength of the carbonated granular material and concrete and/or mortar thus obtained, use of this additive also has surprisingly positive consequences in further suppressing the leaching out of chromium and molybdenum from the carbonated granular material.
- Advantageously, said carbonated granular material may contain at least 2 wt. %, even more preferably at least 3 wt. % and most preferably at least 4 wt. % of carbonates produced during the carbonation step. A good cohesion of the aggregated solid slag particles in each grain is thus ensured.
- Advantageously, said carbonation step may be performed in a continuous counter current flow process. Also, advantageously, said carbonation step may be artificially accelerated, for example, by carbonating with a gas, such as for instance a flue gas, comprising at least 5 vol.%, preferably at least 8 vol.% and more preferably at least 10 vol.% carbon dioxide. Both these features help achieving a more complete carbonation of the steel slag particles. Carbonating with industrial flue gases moreover provides an advantageous use to carbon dioxide that normally would otherwise be directly emitted into the atmosphere as a greenhouse gas.
- Preferably, after said carbonation said gas may still be used to reduce the alkalinity of effluent waters having a pH higher than 11. Handling steel slag, in particular when cooling them and crushing and sieving them, often produces, as a waste product, such highly alkaline effluent waters, with a high content in calcium, sodium, magnesium and/or potassium ions. Bubbling this gas through such effluent waters will further reduce its carbon dioxide content, while simultaneously reducing their alkalinity, reducing the environmental impact of both.
- Advantageously, said gas may comprise less than 30 vol.%, preferably less than 25 vol.% and more preferably less than 20 vol.% carbon dioxide. Also advantageously, said carbonation step may be performed at a temperature of between 10 and 100°C, in particular at a temperature lower than 80°C, and more particularly at a temperature lower than 60°C. This corresponds to the carbon dioxide content and temperature of flue gasses from a wide range of industrial processes, thus allowing the use of the process of the invention for carbon dioxide capture in those industrial processes with a minimum of special arrangements.
- Advantageously, said carbonation step may be performed at a pressure lower than 10 bars and preferably substantially at ambient pressure. Besides requiring less complex installations, and lower energy consumption, it has been found by the inventors that, surprisingly, such low pressure carbonation has positive effects on the strength of the carbonated steel slag and, above all, on its leaching behaviour. Presumably, a low pressure promotes crystal growth instead of crystal nucleation, this latter being known to give rise to very small carbonate crystals characterised by poor binding properties. Apparently, low-pressure carbonation produces larger carbonate crystals, which strengthen the steel slag particles, and also entrap heavy metals, such as chromium or molybdenum, within the particles. Moreover, at such low pressures, the carbonation of silicate phases present in eventually added cement remains limited. Such a carbonation of the silicate phases (e.g. alite, belite) could cause a drop in the pH value, which in turn could possibly reduce the retention of heavy metals.
- Advantageously, said steel slag particles may comprise in particular at least 3000 ppm, more particularly at least 5000 ppm of chromium. Stainless steel slag normally contains significant amounts of heavy metals, complicating its disposal for environmental and public health reasons. By the process of the invention, it is possible to productively use this otherwise troublesome waste as secondary material, e.g. synthetic sand, for the production of mortar or concrete exhibiting satisfactory retention of those heavy metals. In particular, the process of the inventions appears to be particularly advantageous for the treatment of a fine stainless steel slag fraction comprising at least 100 ppm, in particular at least 1000 ppm, and more particularly at least 2500 ppm of molybdenum. Such high molybdenum concentrations are becoming increasingly common in stainless steel slag due to quality requirements, and until now have further complicated the disposal of such slag.
- Advantageously, a water soluble barium compound, such as, for example, barium hydroxide, barium chloride, and/or their byproducts, may be added to the steel slag particles prior to said carbonation step. Such an additive further decreases the leaching out of heavy metals, such as chromium and molybdenum, from the product of the method of the invention.
- Advantageously, a base, in particular sodium and/or potassium hydroxide, is added to the steel slag particles prior to said carbonation step, in order to counteract the pH decrease due to carbonation and, if possible, buffer the carbonated steel slag particles at a pH higher than 11.5, more particularly higher than 12. It has been found that the chromium and molybdenum leaching is lowest if the pH is maintained roughly above 12, in particular between 12 and 13. Moreover, this additive has also been found to facilitate the hydration of amorphous calcium and magnesium oxides in said fine steel slag fraction.
- Advantageously, said steel slag particles may contain at least 3 wt. %, preferably at least 5 wt. % and more preferably at least 7 wt. % of γ-dicalcium silicate.
- The present invention also relates to a carbonated granular material produced according to the process of the invention, as well as to a carbonated granular material of aggregated steel slag particles containing a significant amount of γ-dicalcium silicate, in particular at least 3 wt. %, preferably at least 5 wt. % and more preferably at least 7 wt. %, and bound within each grain by a solid matrix comprising at least calcium and/or magnesium carbonates.
- Advantageously, said steel slag particles may be packed within each grain with a packing density not lower than 5% less than the maximum Proctor density, as determined by Proctor compaction tests according to ASTM D698 / AASHTO T99 carried out on said steel slag particles.
- Advantageously, the carbonated granular material may have a bulk density lower than 1800 kg/m3, preferably lower than 1600 kg/m3 and more preferably lower than 1500 kg/m3. While it is advantageous, under most circumstances, to achieve as close and dense a packing as possible, the carbonated granular material thus obtained will remain a lightweight aggregate, which presents advantages of its own in its use in concrete and mortar mixtures, such as that of allowing the building of strong, yet lightweight structures.
- The present invention also relates to process for producing mortar or concrete by mixing the carbonated granular material with at least a hydraulic binding agent and with water.
- When weight percentages are given in the present specification, these are percentages by dry weight.
- A particular embodiment of the invention will now be described illustratively, but not restrictively, with reference to the following figures:
-
Fig. 1 is a flow chart representing a process for separating a fine stainless steel slag fraction for use with a particular embodiment of the method of the invention; -
Fig. 2 is a diagram representing the phase transitions during the cooling of dicalcium silicate; -
Fig. 3 is a schematic diagram representing a particular embodiment of the method of the invention; -
Fig. 4 represents comparative grain size distribution curves; -
Fig. 5 represents wetting and drying curves for untreated steel slag particles; and -
Fig. 6 represents wetting and drying curves for carbonated grains of aggregated steel slag particles. -
Fig. 1 illustrates a process for separating a fine fraction of stainless steel slag particles. This fine fraction is rich in γ-dicalcium silicate, and presents water absorption properties that normally prevent it being used in mixtures with hydraulic binding agents, such as ordinary Portland cement. In this separation process, the molten lime-silicate slag of astainless steel furnace 1 is emptied inbuckets 2, and transported in thesebuckets 2 to coolingpits 3, in which it is left to slowly cool and solidify. As the cooling is comparatively slow, the slag will not solidify nearly entirely in an amorphous phase, like GBFS, but to a large extent in crystalline phases instead. A significant component of lime-silicate slag is dicalcium silicate (CaO)2SiO2. As crystalline dicalcium silicate cools down, it goes through several polymorphic forms as illustrated inFig. 2 : - α with hexagonal crystal structure,
- aH' with orthorhombic crystal structure,
- αL' with orthorhombic crystal structure,
- β with monoclinic crystal structure, and
- γ with orthorhombic crystal structure.
- With pure dicalcium silicate under laboratory conditions, the transition from αL'-dicalcium silicate to β-dicalcium silicate will occur at 675°C, then to be followed by the transition from β-dicalcium silicate to γ-dicalcium silicate at 490°C. As the transition from β-dicalcium silicate to γ-dicalcium silicate involves an increase of 12% in volume due to their different crystal structure, it will break up the dicalcium silicate crystals. This pulverizes a fraction of the slag. The transition also causes microcracks in the fine γ-dicalcium silicate grains, which appears to explain why this fine dust can absorb and retain large quantities of water. These water absorption properties make this fine γ-dicalcium silicate dust highly unsuitable for most uses in construction.
- Since even with the addition of chemical stabilisers and other measures known to the skilled person, it appears very difficult to completely prevent the formation of γ-dicalcium silicate in mainly crystalline lime-silicate slag, and since in any case these measures could interfere with the economical operation of the
furnace 1, it has been proposed to extract a fine fraction of the slag, because, due to the grain fracture linked to the γ-β transition, this fine fraction is enriched in γ-dicalcium silicate. - In the process illustrated in
Fig. 1 , molten slag is extracted from thestainless steel furnace 1 and brought to coolingpits 3. After cooling, the solidified slag will be dug from thesecooling pits 3 and fed through ahopper 4. Thehopper 4 comprises a grid for stopping alloversized slag pieces 6, in this particular case those bigger than 300 mm. As oversized pieces could damage the crushers used in the later process, theseoversized pieces 6 are removed for later particular treatment, such as breaking with hammers and extraction of large metal fragments before being fed again through thehopper 4. - The slag particles smaller than 300 mm fall through the
hopper 4 onto a first conveyor belt. This first conveyor belt then transports them through a firstmetal handpicking cabin 8 to afirst crusher 9 and afirst sieve 10. In themetal handpicking cabin 8, operators removelarge metal pieces 11 from the slag particles on the conveyor belt 7. After the slag particles are crushed in thefirst crusher 9, they go through thefirst sieve 10 which separates them into three fractions: particles bigger than 35 mm, particles between 14 and 35 mm and particles smaller than 14 mm. The fraction of particles bigger than 35 mm is taken by a second conveyor belt through a secondmetal handpicking cabin 13 and a first metal separatingmagnetic belt 14, wheremore metal pieces first crusher 9. The fraction of particles between 14 and 35 mm goes into asecond crusher 17 and asecond sieve 18, where after being crushed again it is separated into two fractions: a fraction of particles smaller than 14 mm and a fraction of particles bigger than 14 mm. The fraction of particles bigger than 14 mm is taken by a third conveyor belt through a second metal separatingmagnetic belt 20, wheremore metal 21 is removed, and back into thesecond crusher 17. - The fraction of particles smaller than 14 mm from the
first sieve 10, and the fraction of particles smaller than 14 mm from thesecond sieve 18 join again and are put together through thethird sieve 22, which separates them into afraction 23 of particles smaller than 4 mm and a fraction of particles between 4 and 14 mm. - Within this
fraction 23 of particles smaller than 4 mm, afine fraction 24 of particles smaller than 0.5 mm is particularly rich in γ-dicalcium silicate, and is therefore used in a particular embodiment of the process of the invention, illustrated inFig. 3 . - In this process, the particles in said fine stainless
steel slag fraction 24 are first aggregated to form a coarsergranular material 25 with a granulometry between 0 and 4 mm, and then carbonated. The carbonatedgranular material 26 can then be used in a concrete mix with at least a hydraulic binder 27, such as ordinary Portland cement, and water 28, and this as a substitute, for example, of [0-4 mm] porphyry sand. However, since the particles in thefine fraction 24 can form large clods during storage, in particular in the open, in this particular embodiment, a first breaking up step is carried out on those clods before the aggregation step. For this purpose, thefine fraction 24 is dried, then fed through ahopper 29 into arotary harrow 30, and sieved to remove any remaining clods larger than 4 mm, which are then fed back into thehopper 29. - After this breaking up step, the
fine fraction 24 is fed into a disc orpan pelletizer 31, in which the slag particles of thefine fraction 24 are aggregated into a coarsergranular material 25 by the rotation of an inclined disc or pan around itsmain axis 33.Water 34 is sprayed onto thepelletizer 31 for the aggregation of the slag particles. For this, highly alkaline effluent waters from the previous slag treatment steps may be used. To improve the retention of chromium and molybdenum in the finished product, barium hydroxide may be dissolved into thiswater 34 in a concentration of, for example, 0.05-0.5 mole/l, preferably 0.1-0.2 mole/I. However, alternative water-soluble barium compounds, such as barium chloride, may be considered instead, or barium compounds may dispensed with altogether, in particular when chromium and molybdenum leaching is not a particular concern. The purpose of introducing such a barium compound is to form barium molybdate BaMoO4 in the slag particles. Not only has this barium molybdate a low solubility in water, and this even in strongly basic conditions, it also promotes the immobilisation of chromium ions. Furthermore, the addition of water-soluble barium compounds could eventually be expected to improve the mechanical properties of mortar and/or concrete containing the carbonatedgranular material 26. - Fresh steel slag usually contains calcium and magnesium oxides. For a more complete carbonation of the slag, these oxides can be hydrated to convert them into carbonatable calcium and magnesium hydroxides. In this particular embodiment, the
fine fraction 24 is stored in the open for some time before the aggregation and carbonation steps, so that at least a partial hydration happens naturally due to ambient moisture. If the fine steel slag fraction is however so fresh that it has not yet been substantially hydrated by the ambient moisture, it may be advantageous to also dissolve other additives, such as calcium and/or magnesium acetate and/or salts, such as, in particular, calcium chloride, in thewater 34 in order to accelerate this hydration reaction. Tables 1 to 4 show the results of hydration tests on calcinated (and thus substantially calcium and magnesium hydroxide-free) samples of the fine fraction 24:Table 1: Hydration with 20 wt. % pure water Hydration time [min] Mg(OH)2 [wt. %] Ca(OH)2 [wt. %] Total hydroxides [wt. %] 43 0.00 0.00 0.00 236 0.00 0.00 0.00 514 0.08 0.14 0.22 3000 0.11 0.10 0.21 Table 2: Hydration with 20 wt. % of an aqu. solution of 0.5M Mg acetate Hydration time [min] Mg(OH)2 content [ wt. %] Ca(OH)2 content [ wt. %] Total hydroxides [ wt. %] 105 0.89 0.47 1.20 320 0.78 0.63 1.41 1080 0.73 0.32 1.23 2653 0.86 0.40 1.26 4379 0.76 0.53 1.30 Table 3: Hydration with 20 wt. % of an aqu. solution of 0.5M Ca acetate Hydration time [min] Mg(OH)2 content [ wt. %] Ca(OH)2 content [ wt. %] Total hydroxides [ wt. %] 86 1.34 0.08 1.42 163 1.09 0.80 1.89 829 1.07 1.01 2.08 1276 1.11 0.89 2.00 1914 1.02 0.91 1.93 Table 4: Hydration with 20 wt. % of an aqu. solution of 0.5M CaCl2 Hydration time [min] Mg(OH)2 content [ wt. %] Ca(OH)2 content [ wt. %] Total hydroxides [ wt. %] 84 0.00 0.00 0.00 776 0.00 0.61 0.61 1464 0.30 0.87 1.17 3113 0.16 0.72 0.88 - As can be seen from these results, such additives, dissolved in aqueous solutions can significantly accelerate the hydration of calcium and magnesium oxides to form hydroxides in the fine
steel slag fraction 24. - If the rotation speed and inclination of the
pelletizer 31 are kept constant, the grain size of the coarsergranular material 25 obtained in this aggregation step can be roughly controlled by regulating the flow ofwater 34 and the residence time of the slag particles in thepelletizer 31. After being removed from thepelletizer 31, thegranular material 25 is fed intosieve 35 to remove oversize grains, in this particular embodiment those over 4 mm. Eventually, a fine sieve could also be used to remove undersize grains, for instance those under 1 mm. - Through the flow of
water 34 it is also possible to control the water content of the grains of aggregated fine steel slag particles obtained in this way, and, through it, their Proctor density and packing. By "Proctor density", it is understood the compacted dry volumic mass of these aggregates, as determined, for example, but not necessarily, by the original Proctor compaction test, as described in ASTM D698 / AASHTO T99, which is incorporated by reference, and uses a 4-inch (10.2 cm) diameter mould which holds 1/30th cubic foot (850 cm3) of granular or powdery matter, and calls for compaction of three separate lifts of this granular or powdery matter using 25 blows by a 5.5 Ib (2.49 kg) hammer falling 12 inches (30.5 cm). For this particular embodiment of the process of the invention, the results of original Proctor compaction tests carried out on samples of the finesteel slag fraction 24, and presented in Table 5, have shown a water content of around 22 wt. % to be approximately that ensuring the highest density packing of the steel slag particles of this 0-0.5 mm fraction 24:Table 5: Proctor density in relation to water content of 0-0.5 fraction Water content [wt. %] 13.5 16.7 18.8 22.7 25.8 Dry density [kg/m3] 1625 1685 1690 1700 1625 - It must be noted that the water content corresponding to the highest Proctor density will vary with the mineralogy and size distribution of the particles. For example, tests adding increasing amounts of particles in the 0.5-2 mm fraction of the same slag to the 0-0.5
mm fraction 24 and shown in Table 6 have found steadily decreasing water contents for the optimal Proctor density:Table 6: Water content for maximum Proctor density 0-0.5 mm [wt. %] 0.5-2 mm [wt. %] Opt. moisture [wt. %] 100 0 22 75 25 17 50 50 14 25 75 11 - The water content will also be important for the carbonation of the particles, by facilitating the transport of the carbon dioxide reacting with the particles.
- In the next step, this coarser
granular material 25 is carbonated. In a particular embodiment, this carbonation step may be carried out in a continuous manner, for instance within an inclinedrotating drum 36 with aflue gas supply 37, and aflue gas exhaust 38. Thegranular material 25 is conveyed by gravity against the flow of flue gas in thedrum 36. Said flue gas may be provided by, for instance, an incinerator, a power plant, a blast furnace or a cement kiln, at substantially atmospheric pressure and a temperature of around 50°C, with about 10 Vol.% CO2 and a humidity of 98 %. The carbonation time can be regulated by the dimensions of thedrum 36, its inclination and/or its rotation speed. It has been found that a substantial level of carbonation may be achieved in as little as 10 minutes. Although in this particular embodiment the carbonation is carried out continuously, alternatively it would also be possible to carry out batch carbonation instead. - The flue gas exiting the
rotating drum 36 through theflue gas exhaust 38 still contains a significant amount of carbon dioxide. Since highly basic process water, with a pH value which can exceed 12, may be effluent, for instance, from the previous crushing and washing of the steel slag, this flue gas can still be used to neutralise such effluent process water. - Since the liquid water contained in the
granular material 25 promotes the carbonation of the steel slag particles, the humidity of the flue gas in the drum is preferably controlled so as not to fall below 75%, to prevent drying out thegranular material 25. Moreover, this humidity also ensures a more complete hydration of the calcium and magnesium oxides in the steel slag particles to produce the calcium and magnesium hydroxides which then react with the carbon dioxide in the flue gas to form calcium and magnesium carbonates. - Whereas before the carbonation the grains in the
granular material 25 are still highly friable, after this carbonation step the calcium and magnesium carbonates bind the slag particles in each grain of the resulting carbonatedgranular material 26 together, providing significant mechanical strength. More importantly, these carbonates tend to heal the microcracks in the surface of the slag particles, significantly decreasing their ability to absorb additional water, and thus improving the workability of concrete and mortar mixtures incorporating this carbonatedgranular material 26 as a substitute for, for instance, sand. - The maximum "surface dry" water content of untreated fine steel slag of abovementioned 0-0.5
mm fraction 24 has been measured according to European standard EN 1097-6 (or BS 812: part 2:1975) as being 36 wt. %. That of the same fine slag fraction, carbonated and aggregated, has been measured as 19.5 wt. %. Carbonation thus clearly reduces the water absorption of the steel slag particles. - Comparative tests on the wetting and drying of untreated fine steel slag of abovementioned 0-0.5
mm fraction 24 and the carbonatedgranular material 26 have also been carried out. In each case, the material has been previously dried, weighed, and placed in a fine layer on a sieve. This sieve has then been submerged under water and the total water content after various periods of time determined by the increase in weight of the wet material. The amount of water adsorbed, that is, retained around and between the loose particles and grains, but not within them, is determined in each case by subtracting, from the highest total water content, the previously measured maximum "surface dry" water content of each material. This resulted in 27 wt. % for the untreatedfine fraction 24 and just 5.75 wt. % for the carbonatedgranular material 26. - After 25 minutes' immersion, the sieve with the wet material has then been placed in each case to dry in a hot air oven at 52°C. The total water content after various periods of time drying was then determined in similar way.
- Tables 6 and 7 show the results of these comparative wetting and drying of, respectively, untreated fine steel slag and the carbonated
granular material 26. For each total water content, the "surface dry" equivalent absorbed within the loose particles or grains has been calculated by subtracting from it the previously calculated water content adsorbed onto and between the loose particles and grains. Graphs corresponding to these results are also represented inFigures 5 and6 .Table 6: Wetting and drying of untreated steel slag Time [min] Total water content [wt. %] "Surface dry" equivalent [wt. %] Material on 0,5 mm sieve, wetting 0 0,00 0 5 66,85 39,85 10 64,33 37,33 15 62,08 35,08 20 64,33 37,33 25 62,08 35,08 Material on 0,5 mm sieve, drying (52 °C) 25 62,08 35,08 40 42,70 55 29,78 29,78 70 17,13 17,13 85 5,06 5,06 100 0,00 0,00 115 0,00 0,00 130 0,00 0,00 145 0,00 0,00 Table 7: Wetting and drying of carbonated granular material 26Time [min] Total water content [wt. %] "Surface dry" equivalent [wt. %] Material on 0,5 mm sieve, wetting 0 0,00 0 5 20,89 15,14 10 26,24 21,99 15 24,06 18,31 20 24,46 18,71 25 25,25 19,50 30 25,25 19,50 Material on 0,5 mm sieve, drying (52°C) 30 25,25 19,50 45 17,13 1138 60 6,04 75 1,88 1,88 90 0,89 0,89 105 0,50 0,50 120 0,30 0,30 135 0,30 0,30 150 0,30 0,30 - As can be seen in these tables and graphs, apart from the lower water absorption due to carbonation, the carbonated
granular material 26, because of its better drainage, also has a much lower water adsorption, considerably reducing its weight increase when wet, as well as the range of variation in total water content. This facilitates its handling and transport considerably. Moreover, the carbonatedgranular material 26 shows improved heavy metal retention with respect to carbonated, but non-aggregated stainless steel slag particles, as shown by the results of molybdenum and chromium leaching tests according to DIN 38414-S4 carried out on both materials and reproduced on Table 8:Table 8: Heavy metal leaching in carbonated material Mo Cr [mg/l in leachate] [mg/l in leachate] Non-aggregated, carbonated particles 0.47 0.12 Granular material (first test) 0.20 0.12 Granular material (second test) 0.10 0.06 - Also, the high chemical stability of calcium and magnesium carbonates, compared with calcium and magnesium oxides or hydroxides, ensures the improved durability of the mortar or concrete produced using this carbonated
granular material 26. -
Fig. 3 shows the grain size distribution curve of this carbonatedgranular material 26 compared with that of commercially available 0-4mm porphyry sand 40 for construction. As can be seen in this graph, these materials show very similar grain size distributions. The carbonatedgranular material 26 has a bulk density of around 1350 kg/m3, which is considerably lower than the bulk density of such sand, which is around 1840 kg/m3. However, this is an advantageous side-effect, which can result in a reduction of transportation costs, as well as of the weight of structures built using the carbonatedgranular material 26. - To produce mortar, this carbonated
granular material 26 is mixed with cement and water. Table 9 shows the compositions of three examples, A, B and C of such mortar and of two comparative examples, D and E, of conventional mortar produced using 0-4 mm porphyry sand. Mortar A comprises water, an ordinary Portland cement (CEM I), and a carbonatedgranular material 26, produced without addition of barium compounds and carbonated for approximately 3 hours, whereas mortars B and C comprise water, a carbonatedgranular material 26 produced with addition of barium hydroxide, and, respectively, different types of cement, namely the same ordinary Portland cement (CEM I) as mortar A, and a GGBFS cement (CEM IIIB). The two comparative mortars D and E comprise water, 0-4 mm porphyry sand, and, respectively CEM I, and CEM IIIB. These comparative examples follow the specifications of the EN-196/1 standard, namely, by weight, one part cement, three parts standard sand and half a part water, whereas in the examples containing carbonatedgranular material 26, the lower density of this carbonatedgranular material 26 has been taken into account, so that there is only two parts carbonatedgranular material 26 per part of cement.Table 9: Comparative mortar examples MORTAR CEMENT WATER/CEM. SAND/CEM. GRANULAR RATIO (WT.) RATIO (WT.) MATERIAL/CEM. RATIO (WT.) A CEM I 0.5 0 2 B CEM I 0.5 0 2 C CEM IIIB 0.5 0 2 D CEM I 0.5 3 0 E CEM IIIB 0.5 3 0 - After setting, samples of these mortars A, B, C, D and E have been subjected to mechanical resistance tests. Table 10 shows the results of these mechanical tests:
Table 10: Bending and compression strength of mortar samples MORTAR BENDING STRENGTH [MPA] COMPRESSION STRENGTH [MPA] A 3.98 31.81 B 4.85 28.09 C 4.64 24.04 D 9.30 49.41 E 9.52 46.97 - Although the mechanical properties of the samples produced using the carbonated
granular material 26 appear to be substantially lower than those of the reference samples, they remain adequate for construction applications where those properties are not critical. - The samples of the mortars A, B and C have also been subjected to molybdenum and chromium leaching tests according to DIN 38414-S4. Table 11 shows the results of these tests:
Table 11: Molybdenum and chromium leaching under DIN 38414-S4 MORTAR MOLYBDENUM [MG/L] CHROMIUM [MG/L] A 0.10 <0.10 B <0.10 <0.10 C 0.14 <0.10 - As can be seen from these results, the samples containing the carbonated
granular material 26 present very good chromium and molybdenum retention characteristics, apt to satisfy even some of the most stringent environmental regulations. Whether barium compounds are used or not, these retention properties can also be improved by buffering the pH of the carbonated steel slag particles, so that it remains between 12 and 13. Leaching tests have been carried out on finely ground samples of mortar A in aqueous solutions of increasing acidity. In each test, 10 grams of finely ground mortar have been added to 100 ml of aqueous solution and shaken for 24 hours in a vibrating table. To decrease the pH of the mixture, aqueous solutions with increasing concentrations of nitric acid (HNO3) have been applied.Table 12: Leachate of mortar A under increasing acidity conditions mg/l in leachate % acid (vol.) pH B Na Mg K Ca Cr Mo Ba 0 12.42 8.84 86.30 0.00 129.80 430 0.05 0.04 1 12.00 8.66 120.90 0.00 191.40 2994 0.13 0.15 4.81 3 10.79 20.93 136.80 0.00 153.60 8025 0.50 0.30 4.11 6 8.62 53.60 149.90 265.75 154.85 17295 0.44 0.90 5.91 9 7.85 111.0 223.30 1894.5 179.35 27285 0.03 1.26 12 3.30 255.2 283.75 4111.0 290.70 50050 4.32 0.02 13 1.93 275.5 143.05 1101.0 185.50 14510 69.10 1.50 - Table 12 thus shows how it is preferable to maintain a high pH in the mortar or concrete produced using the method of the invention. This can be achieved. for instance, by dissolving sodium and/or potassium hydroxides in the
water 34 before its use in the aggregation step, and this in a concentration, for example, of about 0.05-0.5 mole/I, preferably 0.1-0.2 mole/I, and/or by using a basic process water effluent resulting, for instance, from slag treatment. - Another possibility is the addition of a small amount, for instance 5 wt. %, of hydraulic binder, in particular of ordinary Portland cement, such as, for example, the abovementioned CEM I cement, to the steel slag particles of the
fine fraction 24 prior to and/or during the aggregation step. Not only does this improve the mechanical properties of the resulting granular material, but also, due to the alkalinity of ordinary Portland cement, it also has an additional buffer action, and it also turns out to have an additional positive effect in reducing the leaching of both chromium and molybdenum. - Although the present invention has been described with reference to specific exemplary embodiments, it will be evident that various modifications and changes may be made to these embodiments without departing from the broader scope of the invention as set forth in the claims. For instance, the water content resulting in the maximum packing density may be determined by alternative tests, such as, for instance, the "Modified Proctor" test, ASTM D1557 / AASHTO T180, also incorporated by reference, which uses the same mould, but different compaction parameters, or other related tests using different moulds, compaction methods, or measuring systems. The carbonation could be also carried out using a chemical agent other than carbon dioxide, or in a state other than gaseous. In order to extract fine metal inclusions, the fine fraction of slag particles may also be more finely ground before the aggregation step. Said aggregation step may also be carried out by other means than the disc or pan pelletizer described hereabove, such as, for instance, a pelletisation press. To decrease the concentration of chromium (VI) in the slag particles, a reducing agent, such as, for example, iron (II) sulphate, in particular heptahydrated iron (II) sulphate (FeSO4.7H2O), may also be added to the slag particles. The duration of the carbonation may be adjusted according to the circumstances, and the carbonation be carried out using different equipment than the rotating drum described hereabove. Accordingly, the description and drawings are to be regarded in an illustrative sense rather than a restrictive sense.
Claims (20)
- A process for producing a granular material (26) for mixing with at least a hydraulic binding agent and with water to produce mortar or concrete, characterised in that it comprises:an aggregation step, wherein steel slag particles from at least a fine fraction (24) of steel slag containing a significant amount of γ-dicalcium silicate are aggregated into larger grains so as to form a coarser granular material (25); anda carbonation step wherein said steel slag particles in said coarser granular material (25) are carbonated by means of carbon dioxide so as to produce a carbonated granular material (26), the grains of which contain said steel slag particles bound to one another by a solid matrix containing carbonates formed during the carbonation step.
- A process according to claim 1, wherein the water content of said larger grains during the aggregation step is controlled, so that, at the end of said aggregation step, it is within a range of 5 wt. %, preferably 3 wt. %, above or below the optimum water content resulting in a maximum dry density in a Proctor compaction test performed in accordance with ASTM D698 / AASHTO T99 on the particles used to produce the larger grains.
- A process according to any one of the previous claims, characterised in that said steel slag particles have sizes not larger than x, said x being not larger than 4 mm, preferably not larger than 3 mm, more preferably not larger than 2 mm, and most preferably not larger than 1 mm.
- A process according to claim 3, characterised in that said grains have sizes up to and including y, y being larger than 2x, preferably larger than 3x, more preferably larger than 4x and most preferably larger than 5x.
- A process according to claim 4, characterised in that y is smaller than 25 mm, preferably smaller than 20 mm and more preferably smaller than 15 mm.
- A process according to any one of the previous claims, characterised in that said coarser granular material (25) is agitated during said carbonation step, preferably in a substantially continuous manner.
- A process according to any one of the previous claims, characterised in that a hydraulic binder, in particular ordinary Portland cement, is added to said steel slag particles prior to and/or during said aggregation step, in particular with a weight ratio to the steel slag particles between 1 and 10%.
- A process according to any one of the previous claims, wherein said carbonation is carried out using a gas, such as for example a flue gas, comprising at least 5 vol. %, preferably at least 8 vol. % and more preferably at least 10 vol. % of carbon dioxide.
- A process according to claim 9, wherein said gas is subsequently used to lower the pH of an effluent water having a pH higher than 11.
- A process according to any one of claims 9 or 10, wherein said gas comprises less than 30 vol. %, preferably less than 25 vol. % and more preferably less than 20 vol. % of carbon dioxide.
- A process according to any one of the previous claims, characterised in that said steel slag particles are stainless steel slag particles, comprising in particular at least 3000 ppm, more particularly at least 5000 ppm of chromium.
- A process according to any one of the previous claims, characterised in that said stainless steel slag particles comprise at least 100 ppm, in particular at least 1000 ppm, and more particularly at least 2500 ppm of molybdenum.
- A process according to any one of the previous claims, characterised in that a water soluble barium compound is added to the steel slag particles prior to at least said carbonation step.
- A process according to any one of the previous claims, characterised in that a base, in particular sodium and/or potassium hydroxide, is added to the steel slag particles prior to at least said carbonation step, in order to counteract an increased acidity due to the carbonation step, preferably to buffer the carbonated steel slag particles at a pH higher than 11.5, more particularly higher than 12.
- A process according to any one of the previous claims, characterised in that said steel slag particles contain at least 3 wt. %, preferably at least 5 wt. % and more preferably at least 7 wt. % of γ-dicalcium silicate.
- A carbonated granular material (26) with grains comprising aggregated steel slag particles containing a significant amount of γ-dicalcium silicate, in particular at least 3 wt. %, preferably at least 5 wt. % and more preferably at least 7 wt. %, and bound within each grain by a solid matrix comprising at least calcium and/or magnesium carbonates.
- A carbonated granular material according to claim 17, wherein said steel slag particles are packed within each grain with a packing density not lower than 5 % less than the maximum Proctor density, as determined by a Proctor compaction test according to ASTM D698 / AASHTO T99 carried out on said steel slag particles.
- A carbonated granular material (26) according to claim 17 or 18, with a bulk density lower than 1800 kg/m3, preferably lower than 1600 kg/m3 and more preferably lower than 1500 kg/m3.
- A process for producing mortar or concrete by mixing a carbonated granular material (26) according to any one of claims 17 to 19 with at least a hydraulic binding agent and with water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20090702966 EP2238087B1 (en) | 2008-01-15 | 2009-01-15 | Process for producing a granular material |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2008/050411 WO2009089906A1 (en) | 2008-01-15 | 2008-01-15 | Process for producing mortar or concrete |
PCT/EP2009/050433 WO2009090219A1 (en) | 2008-01-15 | 2009-01-15 | Process for producing a granular material |
EP20090702966 EP2238087B1 (en) | 2008-01-15 | 2009-01-15 | Process for producing a granular material |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2238087A1 EP2238087A1 (en) | 2010-10-13 |
EP2238087B1 true EP2238087B1 (en) | 2011-08-03 |
Family
ID=39387257
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20090702966 Active EP2238087B1 (en) | 2008-01-15 | 2009-01-15 | Process for producing a granular material |
Country Status (9)
Country | Link |
---|---|
US (1) | US8623134B2 (en) |
EP (1) | EP2238087B1 (en) |
AT (1) | ATE518813T1 (en) |
BR (1) | BRPI0906852A2 (en) |
CA (1) | CA2712063C (en) |
DK (1) | DK2238087T3 (en) |
ES (1) | ES2371048T3 (en) |
WO (2) | WO2009089906A1 (en) |
ZA (1) | ZA201005073B (en) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009132692A1 (en) * | 2008-04-28 | 2009-11-05 | Carbstone Innovation Nv | Production of an article by carbonation of alkaline materials |
NL2007190C2 (en) * | 2011-07-28 | 2013-01-29 | Etna B V | METHOD AND APPARATUS FOR TREATMENT OF A MELTING SLIP |
EP2771305B9 (en) * | 2011-10-26 | 2020-03-25 | Carbstone Innovation NV | Method for producing a bonded article comprising a press-moulded, carbonated granular material |
US8845940B2 (en) | 2012-10-25 | 2014-09-30 | Carboncure Technologies Inc. | Carbon dioxide treatment of concrete upstream from product mold |
BR112015018518A2 (en) | 2013-02-04 | 2017-07-18 | Coldcrete Inc | system and method for applying carbon dioxide during concrete production |
US9108883B2 (en) | 2013-06-25 | 2015-08-18 | Carboncure Technologies, Inc. | Apparatus for carbonation of a cement mix |
US9376345B2 (en) | 2013-06-25 | 2016-06-28 | Carboncure Technologies Inc. | Methods for delivery of carbon dioxide to a flowable concrete mix |
US10927042B2 (en) | 2013-06-25 | 2021-02-23 | Carboncure Technologies, Inc. | Methods and compositions for concrete production |
US20160107939A1 (en) | 2014-04-09 | 2016-04-21 | Carboncure Technologies Inc. | Methods and compositions for concrete production |
US9388072B2 (en) | 2013-06-25 | 2016-07-12 | Carboncure Technologies Inc. | Methods and compositions for concrete production |
WO2015123769A1 (en) | 2014-02-18 | 2015-08-27 | Carboncure Technologies, Inc. | Carbonation of cement mixes |
CA2943791C (en) | 2014-04-07 | 2023-09-05 | Carboncure Technologies Inc. | Integrated carbon dioxide capture |
EP2990393A1 (en) | 2014-08-29 | 2016-03-02 | Recoval Belgium | Method for producing a carbonate bonded, press-moulded article |
WO2016087006A1 (en) * | 2014-12-05 | 2016-06-09 | Recoval Belgium | Method for producing a shape retaining mass |
AU2017249444B2 (en) | 2016-04-11 | 2022-08-18 | Carboncure Technologies Inc. | Methods and compositions for treatment of concrete wash water |
EA201991991A1 (en) * | 2017-03-23 | 2020-05-15 | Солидия Текнолоджиз, Инк. | MINERAL ADDITIVES AND MANUFACTURE OF LIGHT COMPOSITE MATERIALS FROM CARBONIZABLE CALCIUM SILICATE |
CA3068082A1 (en) | 2017-06-20 | 2018-12-27 | Carboncure Technologies Inc. | Methods and compositions for treatment of concrete wash water |
US11254028B2 (en) | 2019-05-20 | 2022-02-22 | Saudi Arabian Oil Company | Systems and processes for accelerated carbonation curing of pre-cast cementitious structures |
EP3757083A1 (en) | 2019-06-26 | 2020-12-30 | ORBIX Productions | Method for producing a carbonate bonded, compacted article |
CN111847941B (en) * | 2020-08-12 | 2021-03-05 | 河北蓝海智投环保科技有限公司 | Method for digesting free calcium oxide in steelmaking fly ash |
WO2022153231A1 (en) * | 2021-01-15 | 2022-07-21 | Addforce Services Ltd | Slag processing |
CN114990329B (en) * | 2022-05-26 | 2023-10-24 | 中南大学 | Method for preparing high-strength lightweight aggregate by pellet roasting method |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59223261A (en) * | 1983-05-30 | 1984-12-15 | 住友セメント株式会社 | Cement composition, cement hardened body and manufacture of gamma-c2s |
JPS63242950A (en) * | 1987-03-30 | 1988-10-07 | 角田 正男 | Concrete aggregate made from blast furnace slag dust |
US5421880C1 (en) * | 1994-01-14 | 2001-06-05 | Texas Industries Inc | Method and apparatus for using steel slag in cement clinker production |
AT406262B (en) * | 1998-06-29 | 2000-03-27 | Holderbank Financ Glarus | METHOD AND DEVICE FOR GRANULATING AND CRUSHING LIQUID SLAG |
JP4507298B2 (en) * | 1999-07-14 | 2010-07-21 | Jfeスチール株式会社 | Slag component elution control method |
JP4267446B2 (en) * | 2001-08-21 | 2009-05-27 | 電気化学工業株式会社 | Cement admixture, cement composition, and neutralization suppression method using the same |
JP2003212617A (en) * | 2002-01-25 | 2003-07-30 | Denki Kagaku Kogyo Kk | Hydraulic substance composition for carbonated hardened body and method for manufacturing carbonated hardened body by using the same |
JP3844457B2 (en) * | 2002-07-19 | 2006-11-15 | 電気化学工業株式会社 | Cement admixture and cement composition |
BR0306767A (en) * | 2003-10-16 | 2005-06-07 | Tubarao Siderurgica | Process of economical reuse of steel slag through inerting (aeration with wetting) |
WO2009089907A1 (en) * | 2008-01-15 | 2009-07-23 | Recoval Belgium | Process for preparing a foaming slag former, product and use thereof. |
WO2009132692A1 (en) * | 2008-04-28 | 2009-11-05 | Carbstone Innovation Nv | Production of an article by carbonation of alkaline materials |
-
2008
- 2008-01-15 WO PCT/EP2008/050411 patent/WO2009089906A1/en active Application Filing
-
2009
- 2009-01-15 BR BRPI0906852-0A patent/BRPI0906852A2/en not_active IP Right Cessation
- 2009-01-15 ES ES09702966T patent/ES2371048T3/en active Active
- 2009-01-15 US US12/812,912 patent/US8623134B2/en not_active Expired - Fee Related
- 2009-01-15 EP EP20090702966 patent/EP2238087B1/en active Active
- 2009-01-15 DK DK09702966T patent/DK2238087T3/en active
- 2009-01-15 AT AT09702966T patent/ATE518813T1/en active
- 2009-01-15 WO PCT/EP2009/050433 patent/WO2009090219A1/en active Application Filing
- 2009-01-15 CA CA2712063A patent/CA2712063C/en not_active Expired - Fee Related
-
2010
- 2010-07-16 ZA ZA2010/05073A patent/ZA201005073B/en unknown
Also Published As
Publication number | Publication date |
---|---|
EP2238087A1 (en) | 2010-10-13 |
DK2238087T3 (en) | 2011-11-21 |
ZA201005073B (en) | 2011-09-28 |
WO2009090219A1 (en) | 2009-07-23 |
ES2371048T3 (en) | 2011-12-26 |
CA2712063A1 (en) | 2009-07-23 |
WO2009089906A1 (en) | 2009-07-23 |
ATE518813T1 (en) | 2011-08-15 |
US20110017101A1 (en) | 2011-01-27 |
CA2712063C (en) | 2014-03-25 |
BRPI0906852A2 (en) | 2015-07-07 |
US8623134B2 (en) | 2014-01-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2238087B1 (en) | Process for producing a granular material | |
US10207954B2 (en) | Synthetic aggregate from waste materials | |
EP2160367B1 (en) | Process for preparing a filler for asphalt or concrete starting from a slag material | |
EA001799B1 (en) | A settable composition and uses therefor | |
US20140241979A1 (en) | Method for recycling waste water from a stainless steel slag treatment process | |
Saikia et al. | Use of Pb blast furnace slag as a partial substitute for fine aggregate in cement mortar | |
EP3020692B1 (en) | Geosynthsesis binder comprising a calcium- alkaline activator and a silico-aluminous compound | |
EP2305620B1 (en) | The use of a concrete material comprising aggregates, cement and a cement additive comprising a mixture of three zeolites for making a prefab construction material. | |
TWI434818B (en) | Manufacture of artificial stone | |
EP2903756B1 (en) | Method for producing a water barrier material as landfill cover, capping or landfill liner underneath and/or aside a landfill and water barrier material produced thereby | |
WO2015086350A1 (en) | Method for producing a water barrier material as landfill cover, capping or landfill liner underneath and/or aside a landfill and water barrier material produced thereby | |
BE1024612B1 (en) | Process for producing a mass retaining a shape | |
JP6292257B2 (en) | Hydrated solidified product using desulfurized slag | |
FR2689120A1 (en) | Stabilising incinerated household waste residue - by adding hydraulic binder to prevent release of toxic material during lixiviation | |
KR100528539B1 (en) | Process for the conversion of iron bearing residues into a synthetic rock | |
JP2006240907A (en) | Cement recovery method, cement recovered by the method, and method of reusing cement | |
JPH04118087A (en) | Method for treating dust containing salt from incineration field | |
JP2003306372A (en) | High quality concrete | |
JP2009078932A (en) | Hydrated solidified body, method of manufacturing the same and marine structure | |
JP2005029404A (en) | Cement composition | |
JP2004105783A (en) | Solidification material and solidification method for soil | |
JP7120950B2 (en) | Method for producing fly ash mixed material | |
JP2003235343A (en) | Method for producing porous granular body having raw material inorganic waste | |
JP4535737B2 (en) | Manufacturing method of cured body and cured body obtained by the manufacturing method | |
JP3316546B2 (en) | Manufacturing method of self-filling concrete |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20100802 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA RS |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602009002007 Country of ref document: DE Effective date: 20110929 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2371048 Country of ref document: ES Kind code of ref document: T3 Effective date: 20111226 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20110803 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111205 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111203 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111103 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111104 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20120504 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602009002007 Country of ref document: DE Effective date: 20120504 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120131 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120115 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130131 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110803 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090115 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: HC Owner name: ORBIX SOLUTIONS; BE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: RECOVAL BELGIUM Effective date: 20170913 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: HC Owner name: ORBIX SOLUTIONS; BE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGEMENT NOM PROPRIETAIRE; FORMER OWNER NAME: RECOVAL BELGIUM Effective date: 20170904 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD Owner name: ORBIX SOLUTIONS, BE Effective date: 20180103 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602009002007 Country of ref document: DE Owner name: ORBIX SOLUTIONS, BE Free format text: FORMER OWNER: RECOVAL BELGIUM, 6240 FARCIENNES, BE Ref country code: DE Ref legal event code: R082 Ref document number: 602009002007 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A Owner name: ORBIX SOLUTIONS Effective date: 20190128 |
|
REG | Reference to a national code |
Ref country code: LU Ref legal event code: HC Owner name: ORBIX SOLUTIONS; BE Free format text: FORMER OWNER: RECOVAL BELGIUM Effective date: 20190116 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20230126 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20230124 Year of fee payment: 15 Ref country code: IT Payment date: 20230120 Year of fee payment: 15 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230527 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20231213 Year of fee payment: 16 Ref country code: FR Payment date: 20231213 Year of fee payment: 16 Ref country code: FI Payment date: 20231228 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20231213 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20240125 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240209 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20240118 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240129 Year of fee payment: 16 Ref country code: GB Payment date: 20240123 Year of fee payment: 16 |